JPS625940B2 - - Google Patents

Description

[Detailed description of the invention]

O,O,O',O'-tetramethyl O,O'-thiodi-p-phenylene phosphorothioate is disclosed in U.S. Pat. It is disclosed as an insecticide in each specification of the same No. 3459856. The insecticide was made as cubes of rubber pellets and plaster of paris that floated over mosquito breeding sites in the water. However, these latter formulations were not particularly effective in controlling mosquitoes. The present invention provides an insecticidal effective amount of O, O, O', O'-tetramethyl as an essential active ingredient.
Dogs consisting of novel dry-mixed extrudable and extruded polyvinyl chloride resin compositions containing O,O'-thiodi-p-phenylene phosphorothioate and having long-lasting insecticidal activity and low toxicity to mammals. and a flexible collar for controlling fleas for cats. The flexible collars of the present invention are generally manufactured in a final form such as a flexible extruded sheet, strip, swatch, etc., and are used to treat insecticides, especially flea killers, pet animals, especially dogs and cats, and livestock. It is particularly suitable for use in the manufacture of collars. The polyvinyl chloride resin contained in the flexible collar product of the present invention is solid at room temperature. These resins have weight average molecular weights of 60,000 to 280,000, and AST
Method D-1243-58T of M. has an intrinsic viscosity of about 0.5 to 1.2 as measured by Method A. In this method, the intrinsic viscosity of a solution of 0.2 g of resin dissolved in 100 ml of cyclohesaquinone is measured at 30°C. The resin used in the manufacture of the flexible collar of the present invention is a polyvinyl chloride resin having the molecular weight and viscosity measurements described above. According to the present invention, the weight average molecular weight is from 60,000 to
280,000, preferably 80,000 to 230,000 and an intrinsic viscosity of about 0.5 to 1.2, preferably 0.67 to 1.07, and O,O,O′,O′-tetramethyl O,O-thiodi-p-phenylene About 13-50% by weight of phosphorothioate, preferably 18
A flexible collar for flea control consisting of a resin composition containing ~50% by weight is designed to protect against pests, especially fleas, namely the dog flea (Ctenocephalides) that attacks pets and livestock.
It has been found to be highly effective in controlling fleas such as C. canis and Ctenocephalides felis. O,O,O',O'-tetramethyl O,O'-thiodi-p-phenylene phosphorothioate is not only an excellent insecticide, but also a preferred extrudable and extrudable composition of the present invention. It has surprisingly been found to be used exclusively as both an insecticide and a plasticizer in manufacturing. A preferred composition is O,
O,O′,O′-tetramethyl O,O′-thiodi-
p-phenylene phosphorothioate 36-50% by weight
Average molecular weight 60000~280000, preferably 80000~
230000 and intrinsic viscosity about 0.5-1.2, preferably
About 45-63% by weight of polyvinyl chloride having a polyvinyl chloride of 0.67-1.07, 1-3% by weight of a heat stabilizer for resins and about 100% by weight of a lubricant.
Contains 0.0-2.0% by weight. Although these preferred compositions are preferably free of other and/or secondary plasticizers and pesticides, said preferred compositions may contain small amounts, e.g. 0.1-2.0% by weight, of organic or inorganic pigments. . If pigments are used, the percentage of resin in the composition can be adjusted to compensate for the added pigment. Other preferred extrudable compositions of the invention include O,O,O',O'-tetramethyl, O,O'-
Thiodi-p-phenylene phosphorothioate approx. 13
~40% by weight, preferably 18-40% by weight, molecular weight
400 to 1000, and preferably epoxidized soybean oil, octyl epoxytoleate [Flexol, a product of Union Carbide Company]
) EP-8], a plasticizer selected from the group consisting of epoxidized linseed oil, epoxidized tall oil ester, and epoxidized butyl ester of linseed oil acid.
22.5-7.6% by weight, 1-3% heat stabilizer for resin,
Lubricant 0.0-2.0% by weight, and weight average molecular weight
60000-280000, preferably 80000-230000 and
ASTM Method D-1243-58T--Contains 47.4-63.5% by weight, preferably 47.4-58.5%, by weight of a polyvinyl chloride resin having an intrinsic viscosity of about 0.5-1.2, preferably 0.67-1.07, as measured by ASTM Method D-1243-58T-Method A. These compositions may also contain 1.0-2.0% by weight of organic or inorganic pigments. As with other preferred compositions, the addition of pigment is matched by adjusting the resin content accordingly. Still other preferred compositions of the present invention include:
O, O, O', O'-tetramethyl O, O'-thiodi-p-phenylene phosphorothioate 32-40
6.5-2.75% by weight of dioctyl phthalate, such as di-n-octyl phthalate or di(2-ethylhexyl phthalate), 1-3% by weight of heat stabilizers for resins, 0.0-2.0% by weight of lubricants. , and weight average molecular weight 60000~280000 preferably 80000~
230000 and ASTM Method D-1243-58T--Method A: about 0.5 to 1.2, preferably
Polyvinyl chloride resin with 0.67~1.07 52.25~
Contains 60.5% by weight. Fill in the resin concentration appropriately and add either organic or inorganic pigment from 0.1 to
0.5% by weight may be added. Among the heat stabilizers that can be used in the compositions of the invention are:
There are organometallic stabilizers that are commonly used in the production of extrudable polyvinyl chloride resins. These include organotin stabilizers; organobarium, cadmium and lead stabilizers; zinc and calcium salts, and mixtures of organobarium and cadmium stabilizers. Examples of lubricants that can be used in the compositions of the invention include calcium stearate, stearic acid, paraffin wax, magnesium stearate, aluminum stearate, amide wax, low molecular weight polyethylene and lead stearate when using lead stabilizers. There is. Pigments that may be added to the extrudable compositions of the present invention include inorganic pigments such as carbon black and titanium dioxide, and organic pigments such as quinacridones, anthraquinones, resolvin and alizarin maroon. Examples of polyvinyl chloride resins that can be used in producing the resin composition of the present invention include polyvinyl chloride resins CR80A, FCR, manufactured by Diamond Alkali Co., Ltd.
There are PVC30, PVC33, PVC35, PVC40, and PVC7-44, which have the following characteristics.

[Table] Finely ground low molecular weight solid polyvinyl chloride resin, vinyl stabilizer and lubricant are dry mixed,
Then, the desired amount of O, O, O',
By incorporating O'-tetramethyl, O,O'-thiodi-p-phenylene phosphorothioate as an insecticide and plasticizer, the dry blended extrudable composition of the present invention can be prepared into an extruded sheet. Change it to strips, ribbons, etc. Other plasticizers selected from those mentioned above may be added to produce the desired extrusion composition, and pigments or dyes may also be incorporated into the mixture, if desired. Once the mixture is sufficiently dry mixed, it is charged into an extruder and then extruded at a material temperature of approximately 160°C at the outlet.
During operation, we have found it most desirable to operate at relatively low temperatures to avoid thermal degradation of the phosphorothioate insecticide and plasticizer. The mass extrusion temperature is preferably between about 150-180°C. The extrudates used in this invention are in the form of flexible plastic strips or sheets that are ready to be made into collars for pet animals and livestock. The extruded strip only needs to be attached with a buckle or other fastener to make up the collar. The sheet may of course be cut into strips and a buckling device attached to the strips to make a collar, or the sheet may be cut into strips and one side attached so that the strip can be secured inside a conventional animal collar. Adhesive may be applied to. Unlike many currently available pest control collars and other methods that control pests by fumigation, which utilizes the high vapor pressure of insecticides, the flexible flea control collar of the present invention uses Phosphorothioates have extremely low vapor pressures and achieve control of pests, especially fleas, by local action. Advantageously, the flexible flea control collar of the present invention has very low toxicity to mammals. It has been found that the flexible collar does not cause dermatitis in cats, dogs, or other animals when used in contact with the animal's skin for an extended period of nine months or more. Furthermore, the present flexible collar is fully effective in controlling fleas on cats and dogs during the aforementioned period;
It was also found that this activity showed no signs of decreasing even over a long period of time. The invention is illustrated by the following examples. Example 1 PVC-O,O,O',O'-tetramel, O,
Production of an extrudable resin composition of O'-thiodi-p-phenylene, phosphorothioate. Diamond 40 PVC resin with an intrinsic viscosity of 0.80 and a weight average molecular weight of 120,000 (number average molecular weight of 50,000) measured by AST・MD D-1243-58T (method A)
1000g, stearic acid 5g, carbon black 2
g and 20 g of Thermolite 831-di-n-octyltin maleate polymer PVC heat stabilizer. The mixer was operated at high speed (3600 rom) until the temperature of the mixture reached 79.4°C (175〓), then O,O,O',O'-tetramethyl,
Add 930 g of O,O'-thiodi-p-phenylene, phosphorothioate (90% potency) and continue mixing. When the phosphorothioate addition is complete and the temperature of the mixture reaches 93.3°C (200°C), the mixing speed is reduced to 1800 rpm and the batch is discharged. Once cooled, the hot dry mixture is ready for extrusion. The composition for extrusion is then charged into the feed hopper of the extruder, and the slot width is 0.95 cm (3/8 inch).
Extrude through a horizontal ribbon die having a thickness of 0.32 cm (1/8 inch). From 121℃ (250〓) at rear feed to die band
Extrusion is carried out using a mixture heated to 166°C (330°) and an extrusion stock temperature of 163°C (326°). The extrusion is carried out using a head pressure of 300 psi. Circulating water is used to cool the feed inlet below the feed hopper as well as the extrudate exiting the die. The extruded strips are then cut into 2 foot lengths and buckles are attached to them. The animal collar thus produced does not contain any secondary plasticizers or pesticides other than the phosphorothioate described above. The amount of phosphorothioate is determined by the amount of phosphorothioate in the composition.
47.5% (actually 42.8%). 1000 g of the above PVC resin (intrinsic viscosity 0.80), 20 g of di-n-octyltin maleate polymer, 750 or 800 g of the above phosphorothioate, 0 or 2 g of carbon black, and dioctyl phthalate.
Repeat the above procedure using either 50 g or 150 g of epoxidized soybean oil. The above compositions, all of which result in highly effective and easy to process flea combating animal collars, are expressed in terms of parts by weight of the composition and technical and true weight percent (W/W) for phosphorothioates. show.

[Table] **=True%
Example 2 Effective amount of O,O,O',O'-tetramethyl, O,O'-thiodi-p-phenylene, phosphorothioate as a plasticizer for polyvinyl chloride resin Following the procedure of Example 1, A resin composition containing no second plasticizer is produced. The raw materials used are shown in parts by weight. The data obtained are shown in Table 2 below.
Among the products shown in the table, the above phosphorothioates are technical substances with a potency of 90%.

[Table] Example 3 PVC-O, O, O', O'-tetramethyl, O,
Effect of a second plasticizer on an extrudable resin composition of O'-thiodi-p-phenylene, phosphorothioate.
O, O, as primary plasticizer and flea killer
A resin composition comprising O',O'-tetramethyl O,O'-thiodi-p-phenylene phosphorothioate and a second plasticizer is produced, and the second plasticizer is added to the composition. Examine the effect. The compositions and physical observations related thereto are shown in Table 3 below. From this table, the phosphorothioates mentioned above have 18-40% by weight and a molecular weight of 400-1000, and are selected from epoxidized oils such as soybean oil, linseed oil, tall oil acid esters and linseed oil acid butyl esters. It appears that compositions containing 22.5-7.6% by weight of plasticizer are useful extrudable compositions as animal collars to combat fleas. These data also support the aforementioned 32-40% by weight of phosphorothioate and 6.5% of dioctyl phthalate.
~2.75% have been shown to be extrudable compositions useful in the manufacture of animal collars to combat fleas.

【table】

[Table] Example 4 Activity of O, O, O', O'-tetramethyl, O, O'-thiodi-p-phenylene phosphorothioate flea collar against dog fleas. Adult dog fleas were added to 12 groups of ~4 dogs 3 days before placing a flea collar around each dog's neck.
Gather 100 fish. Each dog is examined daily throughout its body for the presence of fleas. Control of dog fleas observed within one week of the collar being placed on the dog is considered effective control. weekly for each dog.
Let the 100 dog fleas grow again, and then examine the fleas every day. Effective control is considered to be complete control of fleas on all dogs within one week after restocking. All dogs are fed Purina high protein dog food once a day and all dogs are provided with water ad libitum. Keep your dog in a private room with a slatted floor. The composition of the extruded collars tested is shown in Table 4 below in parts by weight and % by weight of phosphorothioate (W/
Indicated by W). The observation results are shown in Table 5. From the data in Table 5, collars 1, 2, 4, 7, 8,
Nos. 9, 10 and 11 appear to be highly effective in controlling fleas on dogs over long periods of 30 weeks or more.

【table】

[Table] Example 5 Mainly following the procedure of Example 4, a polyvinyl chloride resin flea collar having the following composition was made. Polyvinyl chloride resin (intrinsic viscosity 0-80)
51.10% by weight di-n-octyltin maleate polymer
1.02 〃 % Stearic acid 0.26 〃 (Industrial use) O, O, O′, O′-tetramethyl O,
O'-Thiodi-p-phenylene phosphorothioate 47.52% by weight Carbon Black 0.10 This test was carried out on 20 mongrel dogs from USDA licensed handlers.
I got one. Every dog was full of fleas.
Each dog had a different coat color, coat length, sex, and size. All dogs were also vaccinated against distemper prior to arrival. The dogs were housed in a private room with a slatted floor and had free access to water once daily. Five dogs were randomly selected as controls, tagged, checked for fleas, and kept in a private room. Fifteen dogs were fitted with collars of the above composition around their necks and used for testing and evaluation of the composition. For the first 27 weeks, the dogs were tested and reinfected with fleas as in Example 4. After this 27 week period, each dog was reinfected every other week for 53 weeks. All treated dogs were completely (100%) free of fleas within one week after reinfection. The data are shown in Table 6 below. From the table, the control dog (c) continued to be infected with fleas throughout 53 weeks. On the other hand, one of the 15 treated dogs was an exception because its collar was broken, but all the others were free from flea infection.

【table】

【table】

Claims (1)

[Claims] 1. A polyvinyl chloride resin having a weight average molecular weight of 60,000 to 280,000 and an intrinsic viscosity of 0.5 to 1.2, and O, O, O', O'-tetramethyl O, O'- as an essential active insecticide. 1. A flexible collar for flea control for dogs and cats, comprising a dry blended polyvinyl chloride resin composition containing 13 to 50% by weight of thiodi-p-phenylene phosphorothioate. 2 Polyvinyl chloride resin 45-63% by weight, O, O,
O′,O′-tetramethyl O,O′-thiodi-p-
Consisting of a dry blend polyvinyl chloride resin composition comprising 36-50% by weight of phenylene phosphorothioate, 1-3% by weight of stabilizers for the resin, 0.0-2.0% by weight of lubricants and 0-2.0% by weight of pigments. A flexible collar for controlling fleas according to claim 1, characterized in that: 3 Polyvinyl chloride resin has a weight average molecular weight
80,000 to 230,000 and an intrinsic viscosity of 0.67 to 1.07, the flexible collar for controlling fleas according to claim 2. 4. The stabilizer is an organometallic stabilizer, the lubricant is selected from the group consisting of metal stearates, stearic acid, paraffin wax, amide wax, and low molecular weight polyethylene, and the pigment is carbon black, titanium dioxide, quinacridones, 4. A flexible collar for controlling fleas according to claim 3, characterized in that the collar is selected from the group consisting of anthraquinones, lithol rubine, and alizarin maroon. 5. A flexible collar for controlling fleas according to claim 2, wherein the flexible collar is in the form of a flexible extruded strip useful for controlling fleas on dogs and cats. . 6. The flexible collar for controlling fleas according to claim 2, wherein the plasticizer is epoxidized soybean oil.